Theoretical investigation of the CO oxidation on Al12Zr Cluster

Equilibrium geometries of Al12Zr cluster were systematically studied on the basis of density functional theory with generalized gradient approximation. To gain insights into high catalytic activity we use the CO oxidation as a benchmark probe. In Al–Zr bimetallic clusters, Zr site is the catalytically active centre, the adsorption of CO and O2 on the same site respectively (single-site mechanism), a Langmuir-Hinshelwood (LH) mechanism is proposed, which proceed via two steps, CO + O2 → CO2 + O and CO + O → CO2. Two CO oxidation mechanisms of two CO2 molecules as product have been simulated. For the later mechanism, the key step is the O–O bond scission in the OCOO* intermediate, which is significantly accelerated due to the attack of the neighboring CO molecule. The calculated barriers for the later reactions are lower compared with the former reaction. Detailed reaction paths corresponding to this case are calculated. Our study suggests that the CO oxidation catalyzed by Al12Zr cluster is likely to occur at the room temperature.